Water-soluble reactive disazo dyestuffs



United States Patent 3,134,760 WATER-SOLUBLE REACTIVE DISAZO DYESTUFFSAugust Schweizer, Muttenz, and Hanspeter Uehlinger, Basel, Switzerland,assignors to Sandoz Ltd., Basel, witzerland No Drawing. Filed Mar. 2,1961, Ser No. 92,783 Claims priority, application Switzerland Mar. 4,1960 6 Claims. (Cl. 260-146) The present invention relates to reactivemetallizable disazo dyestuffs of the formula and their chromium andcobalt complex compounds, wherein R represents a radical of the benzene,diphenyl or naphthalene series,

R represents a radical of the benzene or naphthalene series, coupledtwice, in both cases in ortho position to hydroxy groups and/ or aminogroups, which latter may be monosubstituted,

x represents a substituent capable of metal complex formation,

One y represents hydrogen or a group containing at least one radical ofthe formula IIIal N=C wherein Halstands forchlorine or bromine, and theother y represents a group containing at least one radical of theformula Hal wherein Hal stands for chlorine or bromine, and wherein R Rand the nucleus A together contain the number of solubilizing groupsnecessary for water-solubility and further substituents if desired.

The process for the production of the new disazo dyestuffs consists incoupling'in either order 1 mol of the diazo compound of an aromaticamine of the benzene, diphenyl or naphthalene series and 1 mol of thediazo compound of an aminobenzene which contains in ortho position tothe amino group a group capable of metal complex formation and may alsocontain further substituents, with 1 mol of a coupling component of thebenzene or naphthalene series which contains two carbon atoms capable ofcoupling in ortho position to hydroxy groups and/ or amino groups, whichlatter may be monosubstituted, upon which the disazo dyestuff obtained,which must contain at least one group introduced before, during or afterthe reaction andbearing at least one radical of the formula Hal whereinHal stands for chlorine or bromine, plus at least the number ofsolubilizing groups necasary for watersolubility, is treated with achromiumor cobalt-yielding agent during or after its formation insubstance or after.

its formation on the fiber.

A procedure which may be adopted is to couple 1 mol of the diazocompound of an aromatic amine of the formula wherein R has theabove-cited meaning and y represents hydrogen or a hydroxy or thiolgroup, a substituent convertible into an amino group which may bemonosub- 3,134,760 Patented May 26, 1964 stituted, or a group combineddirectly or through S, -NH- or N (possibly substituted alkyl) whichcontains at least one radical of the formula Hal wherein Hal stands forchlorine or bromine, with 1 mol of a monoazo compound which may containchromium or cobalt and has the formula Hal wherein Hal stands forchlorine or bromine.

At least one of the radicals y or y must be different from hydrogen. Thedisazo dyestuff obtained, which must contain at least the number ofsolubilizing groups necessary for water-solubility, when y and/or ystand for a hydroxy or thiol group or a substituent convertible into anamino group which may be monosubstituted, is reacted, if necessary afterconversion of the substituent or substituents y and/or y into an aminogroup, with a compound which bears at least two radicals of the formulaHal wherein Hal stands for chlorine or bromine, and treated with achromiumor cobalt-yielding agent during or after its formation insubstance or after its formation on the fiber.

Another procedure which may be adopted is to couple 1 mol of the diazocompound of an aminobenzene of the formula 112 (IV) wherein x, y and Ahave the aforecited meanings, with 1 mol of a monoazo compound of theformula wherein R and R have the above-cited meanings, and to treat inthe way already described the disazo dyestuif obtained, which mustcontain at least the number of solubilizing groups necessary forwater-solubility.

The metallizable reactive dyestuffs and their chromium or cobalt complexcompounds obtainable by the two operating procedures of the processcorrespond in the metal-free state to Formula I. The substituents, whichthe radicals A, R and R may contain according to the given definition,are the sulfonic acid group, an alkylsulfonyl group which may besubstituted on the nitrogen atom (amide, methylamide, ethylarnide,dimethylamide, diethylamide, Z-hydroxyethylamide, di-(2-hydroxyethyl)-amide, 2- or 3-hydroxypropylamide, S-methoxypropylamide, 3- or4-methoxybutylamide, 2-ethoxyethylamide, phenylamide, 2-, 3- or4-methyl-, -methoXy-, -ethoxy-, or -(chlorophenylamide,N-methyl-N-phenylamide, N-Z-hydroxyethyl N phenylamide, benzylamide;cyclohexylamide), or halogen atoms (chlorine, bromine atoms),

lower alkyl or alkoxy groups (methyl, methoxy, ethoxy), nitro groups andacylamino groups (acetyl-, propionyl-, benzoyl-, carbomethoxy-,carbethoxyamino groups).

As compounds which contain at least two radicals of the formula Halwherein Hal stands for chlorine or bromine, the following hcterocycliccompounds are suitable: tetrameric chioroor bromocyan, cyanuricchloride, cyanuric bromide, primary condensation products of a cyanurichalide of the composition wherein Hal represents chlorine or bromine,and z represents the radical of a primary or secondary aliphatic,alicyclic, aromatic or heterocyclic amine, or or" an aliphatic,alicyelic, aromatic or heterocyclic hydroxy or thiol compound, whichradical may be substituted, or more especially the radical of aniline,its alkyl or sulfonic acid or carboxylic acid derivatives, of lowmonoand diaikylamines and the radical of ammonia, further2,4,6-trichloropyrimidine and 2,4,6-tribromopyrimidine and theirderivatives which contain in the 5-position, for example, the followingsubstituents: methyl, ethyl, carboxylic acid amid or sulfonic acid amidewhich may be substituted on the nitrogen atom, carboxylic acid methyl orethyl ester, acyl, e.g. benzoyl, alkenyl, e.g. allyl, chlorovinyl, alkylwhich may be substituted, e.g. carboxymethyl, chloroor bromomethyl andand a methylene group between two pyrimidine nuclei, 2,4,5,6-tetrachloroor tetrabromopyrimidine, 2,6-dichloroor-dibromopyrimidine-4- carboxylic acid ethyl ester,2,4,S-trichloropyrimidine, the 4- or S-carboxylic acid amide or sulfonicacid amide derivatives of 2,6-dichloroor -dibromopyrimidine, 2,5,6-trichloro-4-methylpyrimidine,2,4-dichloro-5-chloromethyl--methylpyrimidine and2,6-dichloro-4-trichloromethylpyrimidine.

The introduction of a dihalogeno-cyanuric radical is carried out to bestadvantage in aqueous medium at about 0 C. and at a weakly acid reaction,e.g. at a pH value between 3 and 5. The cyanuric halide is used as suchin solid form or dissolved in an organic solvent, e.g. acetone. For theprimary condensation products of a cyanuric halide a temperature of 3060C. and a pH value of 4-6 are best, while for di-, triandtetrahalogenopyrimidines temperatures between 40 and 100 C. are the mostsuitable.

In view of the volatility in steam of certain halogenopyrimidines it issometimes advisable to work with Vessels fitted with reflux condensers.The reaction is so conducted that only one halogen atom reacts with anexchangeable hydrogen atom.

The reaction is carried out in weakly alkaline, neutral to weakly acidmedium, but preferably within the pH region of 9 to 3. To neutralize thehydrogen halide which is formed, an acid-binding agent such as sodiumacetate is added to the reaction solution at the beginning of thereaction, or small portions of sodium or potassium carbonate orbicarbonate in solid, powdered form or as an aqueous solution are addedduring the reaction. The addition of small amounts of a Wetting oremulsifying agent to the reaction mixture may accelerate the rate ofreaction. The coupling of the diazo compounds of the amines of FormulaeII and IV with the coupling components is carried out in acid, neutralto alkaline medium at temperatures of 030 C.

Aqueous sodium or potassium hydroxide solutions are also well suited asneutralizing agents.

The conversion of the monoazo compounds or the disazo dyestuffs intotheir chromium or cobalt complex compounds is carried out advantageouslyin aqueous solution or in organic medium, for example in formamide, orin the concentrated aqueous solution of an alkali-metal salt of a lowmolecular aliphatic monocarboxylic acid. It is advantageous to allowamount of a chromiumor cobalt-yielding agent containing less than twobut at least one metal atom to act upon two molecules of the monoazocompound or disazo dyestuff. Suitable compounds of chromium are e.g.chromic fluoride, chromic sulfate, chromic formate, chromic acetate,potassium chromic sulfate or ammonium chromic sulfate. The chromates,e.g. sodium or potassium chrornate or bichromate, are also highlysuitable for metallization.

In this case it is advantageous to Work in strongly caustic alkalinemedium to which reducing substances may be added if necessary.

As cobalt compounds may be used e.g. cobaltous formate, cobaltousacetate and cobaltous sulfate. When metallization is carried out in theconcentrated aqueous solution of an a kali-metal salt of a low molecularaliphatic monocarboxylic acid, water-insoluble metal compounds may alsobe used, for example cobalt hydroxide and cobalt carbonate.

Metallization is carried out with great advantage in aqueous or alkalinemedium, to which the metal compounds are added in presence of compoundssuch as tartaric acid, citric acid or lactic acid which maintain themetals dissolved in complex combination in caustic alkaline medium.

The organic metallizing solution is poured into brine if desired, afterwhich the resulting metal complex compounds are precipitated fromaqueous medium by the addition of salt, then filtered off, washed ifnecessary and dried.

The metal-containing azo dyestutfs obtained are homogeneous metalcomplex compounds in which essentially one metal atom is combined withtwo molecules of disazo dyestuff. The metal complex compounds areso-called 1:2 complexes, wherein one molecule of disazo dyestuif iscombined with about 0.3-0.7 metal atom.

The new reactive dyestuffs and their chromium and cobalt complexcompounds are very suitable for the padding and printing of Wool, silk,leather, synthetic polyamide fibers and fibers of natural or regeneratedcellulose, on which they give brown shades.

The dyeings, paddings and prints obtained, which if necessary may besubjected to an alkaline aftertrcatment at a high temperature andsubsequently soaped, possess good fastness to light, washing, milling,perspiration, rubbing, alkali, crease-resistant finishing and drycleaning. When the dyestuffs have been applied in the metalfree form,they are afterchromed on the fiber and then possess the same goodfastness properties.

In the following examples the parts and percentages are by weight andthe temperatures in degrees centigrade.

Example 1 22.4 parts of 2-amino-4-chloro-1-hydroxybenzene-6- sulfonicacid are stirred into parts of water with 15 parts of 30% hydrochloricacid and diazotized at 05 with a solution of 7 parts of sodium nitritein 25 parts of water. The diazo suspension is run into a solution of 11parts of 1,3-dil1ydroxybenzene and 22 parts of sodium carbonate in partsof water at a temperature of 0-5 The coupling is completed after 3 hoursstirring. The dyestulf is completely precipitated by the addition ofsodium chloride, then filtered olf and washed with sodium chloridesolution.

The filtercake is suspended in parts of Water at 70, and a solution of16 parts of cobalt sulfate in 40 parts of water is added dropwise in 30minutes at 70-75. The pH-value is maintained at 5-6 by the simultaneousdropwise addition of dilute sodium carbonate solution.

After the cobalt sulfate solution has been added, the solution isstirred for 1 hour at 70. The cobalt complex compound is precipitatedwithsodium chloride, filtered off andwashed with sodium chloridesolution. 36.8 parts of 1 amino 3 [2',5, 6' trichloropyrimidyl-(4)-amino]benZene-6-sulfonic.acid are dissolved in 320 parts of water at 60.The solution is cooled to 5 by the addition of ice, 25 parts of 30%hydrochloric acid .are added and then a solution of 7 parts of sodiumnitrite in 25 parts of water in30 minutes. The diazo suspension obtainedis added to the solution of the, cobalt complex compound describedabove. in 3100 parts of water in 15 minutes at a temperature of Tomaintain the pH value of the coupling massat 8.0 -8.5,.sodium carbonateis strewn in. After 3 hours stirring coupling is completed. The -cobaltcomplex compound of .the disazo dyestufi' is completely precipitated bythe addition of sodium chloride, then filtered olf and washed withsodiumchloride solution. The dyestuff, dried with vacuum, is obtained asa dark powdenwhich dissolves in water withadarkbrown coloration.Mercerized cotton sateen is printed with a printing paste of thefollowing composition:

30 parts of the dyestutf obtained according to the particulars givenabove 100 parts of urea 372 parts of water 450 parts of a 3% sodiumalginate thickening parts "of sodium 1'-nitrobenzene-S-sulfonate 33parts of sodium carbonate 1000 parts The dried fabric is steamed for'1015 minutes at 102 104 and subsequently rinsed in cold and warm Water.After soaping at the boil and subsequent'rinsing and drying, abright-print. of good wet and, light fastness is obtained.

Example 2 23.4 parts of2-amino-4-amino-4-nitro-l-hydroxybenzene-6-su1fonic acid are stirredinto 80 parts of Water with 15 parts of 30% hydrochloric acid anddiazotized with a solution of 7 parts of sodium nitrite in parts ofwater at 05. The diazo solution is adjusted with sodium carbonate toreact neutral to Congo red indicator paper and subsequently added to asolution of 22 parts of 1.3-dihydroxybenzene and 44 parts of sodiumcarbonate in 200 parts of water at a temperature of 05. After stirringfor 1 hour the coupling reaction is completed. The dyestufi iscompletely precipitated by the addition of sodium chloride, thenfiltered off and washed with sodium chloride solution until ,no more1.3-dihydroxybenzene is indicated in the filtrate.

The filtercake is stirred into 200 parts of Water at 90. parts ofcrystallized sodium acetate and 30 parts of crystallized chromiumpotassium sulfate are added to the dyestufi suspension, and the mixtureheated for 12 hours with reflux. The chromium complex compound isprecipitated with sodium chloride, filtered off and washed with sodiumchloride solution. 39.2parts of sodium 1- amino 3 [2,5',6'trichloropyrimidyl (4) amino-1 benzene-fi-sulfonate are dissolved in 320parts of water at 60. To the solution, cooled to 5 with ice, are added25 parts of 30% hydrochloric acid and then in 30 minutes a solution of 7parts of sodium nitrite in 25 parts of Water. The diazo suspensionobtained is added to the solution of the above-described chromiumcomplex compound in- 400 parts of water, over 15 minutes at 05. The pHvalue of the coupling mass is maintained at 8.08.5 by strewing in sodiumcarbonate. Afterl hours stirring the coupling reaction is completed. Thechromium complex compound of the disazo dyestuif is precipitatedcompletely by the addition of sodium chloride, filtered off andwashedwith' sodium chloride solution. The dyestufi is dried with vacuumand is obtained as a dark. powder whichdissolves in water with a darkbrown coloration.

Cotton cretonne is printed with a'prlnting paste, of the followingcomposition:

30 parts of the dyestufi obtained according 'to theparticularsgivenaboveparts ofiurea .372 parts of-water '450-parts. of a13% sodium. alginatethickening 15 parts;of-sodium 1-nitrobenzene-3-sulfonate 33. parts ofsodium carbonate 1000 parts The dried" fabric is steamed-for 10-15minutes at 102- 104 and subsequently rinsed, in cold and warm 'water.After 'soaping' at the boil and subsequent rinsing and drying; a reddishbrown print ofgood wet and light fastness is obtained.

Example 3 .precipitated by the addition of sodium chloride, filtered offand washed with sodium chloride solution.

The filtercake is stirred-into 350 parts of Water and the pH adjusted to8.5 by the addition of sodium carbonate. A diazo solution of,23.4 partsof 2-amino-4-nitro-1-hydroxybenzene-6-sulfonic acid, prepared as giveninExample. 2, is then added dropwise, the pH value ofthe coupling massbeing maintained at 8.59 by the addition of sodium carbonate solution.After stirring for 12 hours the disazo dyestuff is precipitated byacidification With 30% hydrochloric acid, filtered off and washed withsodium chloride solution. ,The filtercake is suspended in 400 parts ofwater at 70 and at a pH value of 5 Over 30 minutes a solution of .16.,partsof cobaltous sulfate in 40 parts of water is added dropwise at7075. The pH value is maintained between 5 and: 6 by the simultaneousdropwise addition of a dilute sodium carbonate solution. After thecobalt sulfatesolution. has been .addedthe mixture is stirred furtherfor 1 hour at 70. The cobalt complex compound is precipitated by theaddition of sodium chloride, filtered 0E and washed with sodium chloridesolution. The dyestuif is dried with vacuum and is obtained as a darkpowder which dissolves in water with a dark brown coloration.

A fabric of viscose staple fiber is printed with a printing pasteofthefollowing composition:

30 parts of the dyestuff obtained according to the particulars givenabove 200 parts of urea 272 parts of water 450 parts of a 4% sodiumalginate thickening .15 parts of sodium1-nitrobenzene-3-sulfonate 33parts of sodium carbonate 1000 parts The dried goods are exposed todryheatfor 1' minute at 200 or 10 minutes at .suhsequently'rinsed incoldand warm waterand'soaped at the boil. After further rinsing and.dryingabrown printof. goodwet and light fastness is obtained.

Example 4 To a neutral solution of 23 parts ofI-amino-B-acetylaminobenzene-6-sulfonic acid in 200 parts of water and13.4 parts of 30% sodium hydroxide solution is added a solution of 7parts of sodium nitrite in 25 parts of water. The whole isthen addeddropwise over 30 minutes to 25 parts of 30% hydrochloric acid in 100parts of ice-Water at -5. This diazo suspension is then run into asuspension of 34.1 parts of the monoazo dyestutf, obtained according tothe particulars given in the first paragraph of Example 2, in 250 partsof water at and the pH value of the coupling mass held at 8.5-9.0 by theaddition of sodium carbonate. After stirring for 8 hours at 5-10 thecoupling reaction is completed. The disazo dyestuif is completelyprecipitated with sodium chloride, filtered off and Washed with sodiumchloride solution. The filtercake is stirred into 400 parts of a5 sodiumhydroxide solution and maintained for 1 hour at 95. The deacetylateddisazo dyestufi is precipitated by the addition of sodium chloride,filtered with suction and Washed with sodium chloride solution.

The filtercake is suspended in 400 parts of Water, reacted with acobalt-yielding agent and isolated according to the particulars given inExample 1.

The cobalt complex compound thus obtained is dissolved in 300 parts ofWater and then at a temperature parts of the dyestuff obtained accordingto the particulars given above 200 parts of urea 565 parts of water 200parts of 3% sodium alginate thickening 5 parts of a highly sulfonatedcastor oil 1000 parts The goods are steamed for 2 periods of minuteseach with intermediate cooling.

The following table shows further chromiumand cobalt-containing reactivedyestuffs which are obtainable according to the particulars of Examples1 to 4 Ex. No. Diazo Component 1 Coupling Component Diazo Component 2Reactive System Metal Shade (Iv) (V) (VI) 5 1,3-diaminobenZene-6-1,3-dihydroxybenzene Z-amino-l-hydroxybenzene-2,4,5,(rtetrachloropyrimi- Cr Rcddish sulionic acid. 4-su1tonlc acid.dine. br 6 do do 2-amin0-4-chloro-1-hy- 2,4,6-trichloropyrhnidinc. Or Ddroxybenzene-6-sulf0nic acid. 7 do do 2-amino-1-hydrcxybcnzened0 Co DD,

4-sulfonic acid. 8 "do do 2-amin0-6-nitro-1hydr0Xy-2,4,5,6-tctrach10ropyrimi- C0 D0,

benzene-4-sulionlc acid. dine. Or Do. C0 D0. Cyanuri Go Do. 2,4,,G-tctrachloropyrimi- C0 D0. benzene-B-sulionlc acid. dine. 13 do do2-amino-l-hytroxybenzene- Cyanuric chloride Or Do,

4,6-disuli0nlc acid. 14 do do do 2,4,trtribromopyrimidinefl Cr Redbrown.15 do do z-amino-l-hydroxybenzene- 2,4,5,etetrachloropwimi- Cr Reddish4-su1fon1c acid amide. dine. brown. 16 do do do do Co Brown. 172,6-diamino-naphthalencdo 2-aminc-1-hydroxybenzene-2,4-dichloro-6-(2-hydroxy)- C0 D0,

4,8-disuli'onic acid. 4-Sulf0ni6 acid. ethylainino-1,3,5-triazine. 18 dodo do 2,4-dichloro-tiaminO-l,3,5- Cr Reddish triazine. brown. 19 do dn2-amin0-4 chl0ro-1-hydroxy- 2,4,6-trichloropyrimidinc Or Dbenzene-d-sulionic acid. 20 do ..do d0 2,4,5,6-tetrabromopyrimid- 00Brown.

me. 21 do do 2-amino-G-chloro-l-hydroxydo C0 D benzene-4-sulionic acid.2' (lo do do 2,4-dichloro-(S-ethylamino- Cr Reddish1,3,(i5-triazine-W-sulionic brown. aci 23 do do 2amino4-nitro-l-hydroxy-2,4,5,6-tetrachloropyrimi- Or Do.

benzcne-6-sulr'onic acid. dine. 24 do "d0 do cdO C0 Brown, 25 do do2-amino-G-nitro-l-hydrmy Cyanuric bromide Go Do,

bcnzenct-sulionic acid. 2% do do do 2,4,6-tricl1lor0pyrimidine CrReddisli brown. 27 4.4-diamin0-1.1-dipl1endo Z-amino-l-hydroxybenzcne-2,4-dichl0r0-(rcarb0xy- Co Brown,

yl-3-su1to11ic acid. 4,6-disulfonic acid. methylami-1,3,5-

triazine. 28 do do do 2,4-dichl0r06-phenylamin0- Cr Reddish1,3,(15-triaZinc-3-suli0nic brown. ac: 29 do ..dn2-amino-4-chl0ro-1-hydroxy- 2, i-diehl0r0-5-chl0r0- Or Do.

benzenc-dsulionic acid. mcthyI-G-methyl-pyrirni- (inc. do Cyanuricchloride...- Brown. 2amino-Gchloro-Lhydroxy- 2,4-dibrom0-0-phcnyla C0D0.

bcnzenei-sulfonic acid. 1,3,d5-triazinc-4sulfonic aci 32 do do d02,4-dicl1loro-0-phenylamino- Gr Reddish 1,3,-triaZinc-2-carboxylicbrown. aci 3% do do 2-an1in0-4-nitro-l-hydroxy- 2,5,(HrichloroA-methyl-Cr D0.

benzene-G-sulionic acid. pyrimidine. 34 do do do2,4,6-trichlor0pyrimidine 00 Brown. 35 do do 2-amino-6-nitro-1-hydroxydoC0 D0.

benzene-d-sulionic acid. 36 d0 do do Cyanuric chloride Cr Reddish Abrown. 37 l-arnlnobenzenc-i-sultonic d0 2,6-diamino-l-hydroxyben-2,4,5,6-tctrachloro-pyrimi- Cr Do,

ac I zenc-et-sulionic acid. dine. 38 l-anunobenzeue-Zi-sulionic do do doCo Brown.

Ionic acid.

Ex. No. Diazo Component 1 Coupling Component Diazo Component 2 ReactiveSystem Metal Shade 39 1,3-diaminobenzene-6-sul- 1-amin0-3-hydroxyben-2-amino-1-hydroxybenzcne- 2,4-dichicro-6-di-(fl-hydroxy- 00 Brown.

ionic acid. zene. 4-Sulfonic acid. eti1y1)-aminc-1,3,5-triazme. 40 d0"d0 "d0 2,4,6-trich10ropyrimidine- Ct Raddish rown. 41 -.do .do2amino-4-nitro-1-hydroxy- 2,4,5,6tetrabr0m0pyrimi- Go Do,

benzene-S-suifonic acid. dine. 42 .d0 d0 d0.. .....d0 Or Do. 43 .do "do2-amino-4-chloro-1-hydroxyd0 Or Do.

benzcne-fi-sulionic acid. 44 d0 d0 Z-a iIm-LhydroXybenZene-2,4,5-trich1oropyrimidine Or Do,

-suifonic acid (N -3'- methoxy)-propylamide. 45 .do d0- .do-2,4-dich1oro-6-N-methyl-N- Go Do.

ethyi-amino-l,3,5-triazine- 2-su1fonic acid. 46 "do 1,3-diaminobenzene2-amin0-4nitro-1-hydroxy- 2,4,5,6-tetrach1oropyrimi- Or Do,

benzene-G-suifonic acid. dine. 47 do do 2-amino-G-nitro-l-hydroxydo OrDo,

benzene--sulfonic acid. 48 d0 d0 2-amin0-4-ch1or0-1-hydroxy- Gyamnicchioridc Or Do,

benzene-G-sulfonic acid. dn 2-amin0-6-ch1oro-1-hydroxy-2,4,5,6-tetrabromopyrimi- Or Do.

benzenc-4-su1fonic acid. dine. d0 Z-amino-l-hydroxybenzene- 2,4,6trich1oropyrimidine- Or Do.

4-su1ionic acid. 2-amino-5-hydroxynaph- 2-amino-4nitro-1-hydroxydo CrVioiettish tha1ene-7-su1f nic a id; benzcne-fi suiionic acid. brown.

do 2-amino-6-nitro-l-hydroxy- 2,4,5,6-tctrachloropyrimi- O0 Reddishbenzenei-suiionic acid. dine. brown .....(10 2-amino-4-ch1cro-1-hydroxy-Do.

benzene dsulfonic acid. 54 (in do 2-amino-fi-chioro-1-hydroxy- Do.

' benzene-i-sulfonic acid. 55 1,4-diamin0benzene-2-1,3-dihydroxybenzene-. -a O -0 0 0-1-hydroxy- Brown sulfonic acid.benzene-G-sulfonic acid. 56 1,3-diaminobenzene-6- .-do2-am1n0-6-acetylamino-1- D sulfonic acid. hydrogcybenzene-isuifonicacid. 57 rin do 2-amin0-6-methy1-1- 2,4,5,6tetrachioropyrin1i- C0 D0.

hydroxybenzenc-4- dine. suifom'c acid. 58 (In do do2,4-dichioro-5-chioromethyl- C0 D0.

G-methylpyrimidinc. 59 3-amino-1-(hydroxyd0 2-aminp-1-hydroxybenzenc-2,4,6-trichl0ropyrimidine Go Do,

methyl)-benzene. 4.6;d1sulfonic acid. 60 1.3-diaminobenzenc-6-l-amino-B-hydroxynaph- 2am1no-1-hydroxybcnzene- 2,4-d1 ch10r0fi-Inethyi- C0 Violet sulfonic acid. thacne-afi-disulfonic 4-sngonicacid methylammo-1,3,5-triazine. brown.

8.01 8.1111 8. 61 do Z-methylamino-dhydroxy- Z-anlinoA-nitro-l-hydroxy-2,4-dichloro- 6-ethy1amino- Co violetti h na%htha1ene7-su1fonicbenzene-fi-sulfonic acid. 1,3,5-tr1az1ne. brown. 801 62 d02-phcny1amino-5-hydroxy- ..d0 2,4,6-trichioropyrimidmc Go Do nahthaleneJ-sulfonic 3,01 63; 1,4-diaminobenzene-2-"1,3-dihydr0xy-4chloro- 2-aminc-4-chioro-1-hydroxy-2,4-dich10r0-6-(3-hydroxy)- 00 Brown.

suifonic acid. benzene. benzene-dsulfonic acid.propy1aminc-1,3,5-triazine. 6-1 do 1,3-dihydroxykmethy1- d02,4-dich10r0-6-(3-methoxy)- C0 D0.

benzene. propylamino-1,3,5triazine. 65 do1,3-dihydr0xybenzenez-amino-l-hydroxybenzene- 2,4-dichloro-6-dimethyi-Go Do,

4-S1ig011i0 acid ethylamino-1,3,5-triazine.' am e. 66 do do2-amino-1-hydr0xybenzene- 2,4,5,6-tetrachloropyrimi- C0 D0.

4-su1ionic acid (2-hydine. dxoxy)-ethy1amide. 67 "do; .doZ-amino-l-hydroxybenzenedo C0 D0,

4-sulionic acid-(3-hydroxy)-propyiamide. 68 d0 dcZ-amino-l-hydroxybenzenedo C0 D0.

4'su1fonic acid (2-ei;hoxy)- ethylamide. 6Q rio .....deZ-aminc-l-carboxybenzene- 2,4 dichioro-6-di-(3'-hy- Or D0. 7 fi-suiionicacid. droxypropy1)-amino-1,3,

fi-triazine. 70 do do Z-aminc-i-hydroxybenzene-2,4,6trich1oropyrimidi.ne- 00 Do.

5-su1fonic acid. 71 1,3-diaminobenzene-6-sui- 1,3-diaminc-4-chioroben-2-amino-1-hydroxybenzene- 2,4,5,6-tetrach1oropyrimi- Go Do.

ionic acid. zene. 4-su1fonic acid. dine. 72 do 1,3-diamino-4-mcthy1bendodo 0 zene. 73 do 1,3-dihydroxybenzene 2-amino-1-carbcxybenzenedo C1- D0,

fi-suifonic acid. 74 do do 2-amino-1-carboxybenzene2,4-dich1oro-6-ethy1amino- Or Do.

l,3 ,d5-triazine-2-sulionic aci 75 l-aminonaphthalenei- -do2,6-diamin0-1-hydroxyben- -d0 Go Do,

sulionic acid. zene-4-su1fonic acid. 76 1-amin0benzene-2-su1- do .do2,4,6-trichloropyrimidine. C0 D0.

ionic acid. 77 1-amin0naphtha1ene-3,6- d0 d0 .d0 Cov Do.

disulfonic acid. 78 d0 d0 2,irdiamino-1-hydroxyben- Cyanuric chloride GoDo,

zenci-sulionic acid. 79 2'aminonaphthaiene-4,8- d0 "do2,4dich1oro-6-amino-1,3,5- C0 D0.

disulfonic acid. triazine. 8O 2-amino6-acetyiaminod0 .d02,4,5,6-tetrach1cropyrimi- C0 D0.

. naphthalene-4,8-disuldine.

ionic acid. 81 1-aminobenzene-2,4-disuldo do 2,4,5,6-tetrabromopyrimi-C0 D0.

ionic acid. dine. 82 1-aminobenzene-2,5-disu1- dn2,4,6tribr0mopyrimidine C0 D0.

11 Formulae of representative dyes of the foregoing examples are asfollows:

Example 1 The 1:2 cobalt complex compound of OH OH H038 N=N H $0311 I II O1 01 N=N I Q N-C NHO N Example 2 The 1:2 chromium complex compound ofOH C| H Hogs N=N OH SOSH Cl N=N-Q NJ} NH-C N Example 3 The 1:2 cobaltcomplex compound of OH OH HOaS- N=N H03s- -NH; $0 11 I l 01 NO, N=N I 2K NH-C N C=C/ (E1 ('31 Example 4 The 1:2 cobalt complex compound of OHOH H0 8 N=N OH S 0 11 12 Example 16 The 1:2 cobalt complex compound ofThe 1:2 cobalt complex compound of HO S N=N- OH S0311 01 NO; N=N A -NHO/N HO 3 7 C20 Example 47 The 1:2 chromium complex compound of OH 11TH:

OgN N=N NH1 so l-I C1 S0311 N=N-- g NH-C N Having thus disclosed theinvention what we claim is: 1. A member selected from the groupconsisting of metallizable disazo dyestuffs of the formula (Z-NH) 11-1and their 1:2 cobalt and chromium complex compounds,

wherein R is a member selected from the group consisting ofmonosulfophenyl, disulfophenyl, monosulfonaphthyl, disulfonaphthyl andmonosulfodiphenylyl,

R is a member selected from the group consisting ofmeta-dihydroxyphenyl, meta-diaminophenyl, sulfonatedamino-hydroxynaphthyl, sulfonated lower alkylamino-hydroxynaphthyl,sulfonated phenylaminohydroxynaphthyl, y itself being a member selectedfrom the group consisting of hydroxy, amino, lower alkylamino andphenylamino and being in orthoposition to azo,

L) x is a member selected from the group consisting of hydroxy andcarboxy, Z is a member selected from the group consisting ofdi-halogenoapyrimidyl dihalogeno-4-methyl-pyrimidyl-,trihalogeno-pyrimidy-L, 2,4-dihalogeno-6-methyl-pyrimidyl-5-methylene-,4,6-dihalogeno-l,3,5-tri-azinyl-2-,4-ha1ogeno-6-amino-1,3,5-triazi-ny1-2-, 4-halogeno-6-loweralkylamino-l,3,5-triazinyl-2-,4-halogeno-6-di(loweralkyl)lamino-1,3,5-triaZinyl-2-, 4-halogeno-6-lowerhydroxyalkylamino-1,3,5-triazinyl-2-,

4-halogeno-6-di-(lower hydroxyalkyl)amino-1,3,5-

triazinyl-2-,

4-halogeno-6-lower alkoXyalkylamino-l,3,S-triazin- 4-hialogeno-6-lowercarboxyalkylamino-l,3,5 triazin- 4-halogeno-6-lowersulfoalkylamino-l,3,5-triazin- 4-halogeno-6-N-lower alkyl-N-lowersulfoalkylaminol,3,5-triazinyl-2-,

4-halogeno-6-carboxyphenylamino-1,3,5-triazinyl-2- and 4halogena-6-sulf0phenylamino-1,3,5-triazinyl-2-,

halogen having an atomic Weight between 35 and 81,

and Z being free from further subst-ituents,

t is a member selected from the group consisting of hydrogen, chlorine,methyl, nit-r0, acetylamino and SO' H,

v is a member selected from the group consisting of hydrogen and SO H,and

w is a member selected from the group consisting of hydrogen, chlorine,nitro, methyl, SO H, sulrfonic acid amide, sulfonic acid loweralkylamide, sulfonic acid lower hydroXy-alkylamide and sulfonic acidlower alkoxyalkylamide,

n being One of the integers 1 and 2.

2. The 1:2 cobalt complex compound of 3. The 1:2 cob-alt complexcompound of 4. The 1:2 cobalt complex compound of 5. The 1:2 cobaltcomplex compound of 1-2 01110111111111 COIIlPlfiX COmpOLlIld Of FranceIan. 18, 1960 France Oct. 24, 1960

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF METALLIZABLE DISAZODYESTUFFS OF THE FORMULA